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  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
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  • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
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Definitions

• the present invention relates to post-metallocene compounds.
• the invention also relates to the application of such compounds in catalytic systems suitable for use in polymerisation, such as in polymerisation of olefins.
• catalytic systems allow for the production of polymers having high molecular weight, at particular high polymerisation activity, as well as high degree of incorporation of desired comonomers in copolymerisation reaction of olefins.
• Polymers of ethylene and other olefins are ubiquitously available and find widespread applications.
• typical olefin-based polymers include various types of polymers that are produced by reaction of a particular reaction mixture in the presence of a catalytic system.
• ethylene-based copolymers include for example medium-density polyethylenes (MDPE), linear low-density polyethylenes (LLDPE), polyolefin plastomers (POP), polyolefin elastomers (POE), and ethylene-propylene-diene terpolymers (EPDM).
• MDPE medium-density polyethylenes
• LLDPE linear low-density polyethylenes
• POP polyolefin plastomers
• POE polyolefin elastomers
• EPDM ethylene-propylene-diene terpolymers
• the polymers In order for these polymers to qualify as suitable materials for applications with significant commercial importance, the polymers have to have a particular molecular weight, expressed as the weight-average molecular weight (M w ), such as of at least 10 kg/mol, preferably of at least 50 kg/mol, but even more preferably of at least 100 kg/mol, and may for example be in the range of between 100 kg/mol and 500 kg/mol, to provide a polymeric product that demonstrates desirable product qualities in combination with processability via melt shaping processes, as typically used in shaping of products based on polymeric materials.
• M w weight-average molecular weight
• a further ethylene-based polymer produced using catalytic systems is high- density polyethylene (HDPE), such as for example bimodal HDPE, which is used in for example certain high demanding applications as pressure pipes.
• HDPE high- density polyethylene
• Such bimodal HDPE typically comprises a low molecular weight fraction of ethylene homopolymer, and a high molecular weight fraction ethylene-based copolymer.
• the high molecular weight fraction of such bimodal HDPE typically has an M w of above 100 kg/mol, even above 300 kg/mol, or even above 500 kg/mol.
• UHMWPE ultra-high molecular weight polyethylene
• UHMWPE ultra-high molecular weight polyethylene
• Particular aspects pertaining to the catalyst system employed in the polymerisation of olefins include the activity of the catalyst, the ability of incorporation of comonomers, and the ability to produce a polymer product having a high molecular weight.
• the activity of the catalyst indicates the quantity of polymeric product that is obtained per quantity of catalyst used.
• the ability of comonomer incorporation indicates the quantity of comonomer that is reacted into the polymer when polymerisation takes place at a given quantity of comonomer present in the reaction mixture; due to lesser reactivity of the comonomer vis-a-vis the main monomer.
• a further known trend in preparation of polymers based on olefins in particular in preparation of copolymers based on ethylene and a-olefins such as a-olefins comprising 3-10 carbon atoms, is that the molecular weight of the obtained copolymer decreases with an increase of the content of the comonomer that is built into the polymer chains.
• the challenge that therefore continues to be present is to combine the desirable incorporation of the comonomers in the polymerisation of e.g. ethylene with the desirable high molecular weight.
• catalysts have been developed over the years and have found commercial implementation in various process concepts of polymerisation, and are widely disclosed in literature.
• a particular group of catalysts are single-site catalysts.
• a single catalytically active specie is present, which translates into a narrow polydispersity, which is defined as the molecular weight distribution (M w /M n ), and a narrow composition distribution, which tend to result in particularly desirable mechanical properties of the obtained polymers.
• This category of single-site catalysts includes the group of catalysts referred to as post metallocene catalysts.
• Such post-metallocenes are to be understood to be compounds comprising a discrete transition metal compound, wherein the compound does not comprise cyclopentadienyl or substituted cyclopentadienyl moieties, which are present in metallocene catalysts.
• transition metal compounds containing amine-bisphenolate ligands are known.
• the amine group that connects the aromatic rings of the two phenolate moieties is typically substituted via a hydrocarbon spacer to an electron donating group that can coordinate to the transition metal.
• catalysts which are able to produce amorphous or semi-crystalline polyolefins in high yield, having a high reactivity for comonomer incorporation (like for example copolymerization of ethylene with 1 -hexene or other sterically encumbered olefins) and which is still giving high molecular weight copolymers.
• each of Ri to R12 may individually be a moiety selected from hydrogen, an aryl moiety, an aryl moiety, a halogen, an alkyl or aryl moiety with halogen substituent(s), an alkoxy moiety, a siloxy moiety, or a nitrogen-containing moiety, wherein each R moiety may optionally form a ring structure with an adjacent R moiety;
• each of Ai and A2 may individually be a moiety selected from: o an element of Group 16 of the periodic system; and o a moiety containing an element of Group 15 of the periodic system; preferably wherein Ai and A2 are selected from O or NR 13 , wherein R 13 is an alkyl, aryl or aralkyl moiety, preferably a substituted or unsubstituted phenyl moiety, preferably a p-tolyl moiety; ⁇ T is a divalent hydrocarbyl moiety;
• D is a substituted element of Group 15 or Group 16 of the periodic system, preferably an N(R M )2 or OR M moiety, in which R « is selected to be an alkyl moiety, an aryl moiety, or an aralkyl moiety, preferably R M is a methyl moiety;
• Y is an element selected from Group 15 of the periodic system, preferably N;
• ⁇ Mt is a transition metal, preferably selected from Group 3 or 4 of the periodic system, more preferably selected from Ti, Hf and Zr;
• X is a sigma-bonded ligand, preferably selected from a halogen, an alkyl moiety, an aralkyl moiety, an alkoxy moiety, an aryloxy moiety, and a dialkylamine moiety; and • n is the amount of X ligands bonded to X, preferably n is 1 , 2 or 3.
• each of Ri and R I2 are individually selected to be a moiety selected from t-butyl, adamantyl, 9/-/-carbazole-9-yl, hydrogen, and phenyl.
• Ri and Ri2 may be the same, or Ri and R12 may be different.
• each of R 3 and R10 are individually selected to be a moiety selected from hydrogen, t-butyl and methyl, preferably wherein R 3 and R10 are the same or wherein R 3 and R10 are different. Furthermore, it is preferred that each of R2, R4, Rs, R 6 , R7, Rs, R9 and Rn are hydrogen.
• T is selected from an ethyl moiety (-CH2-CH2-) and an n-propyl moiety (-CH2-CH2-); particularly preferably, T is an n-propyl moiety. Further, it is preferred that Y is nitrogen.
• D may be part of a cyclic structure like pyridyl, tetrahydrofuran, or furane.
• D is 0(CH 3 ) or N (CH 3 ) 2 ;
• T is ethyl or n-propyl
• Ai is O or N(p-tolyl), preferably O;
• A2 is O or N(p-tolyl).
• the invention in a certain embodiment also relates to a catalyst system comprising a compound according to formula 1.
• a catalyst system further comprises an activator, wherein the activator is selected from an aluminoxane compound and a boron-based compound, optionally in the presence of an aluminium alkyl compound.
• Such aluminoxane compound may for example be selected from a methyl aluminoxane, an isobutyl aluminoxane, and a methyl-isobutyl aluminoxanes;
• the boron-based compound my for example be selected from a tris(pentafluorophenyl)borane an a tetrakis(pentafluorophenyl)borate. Suitable examples of such are ammonium salts or trityl compounds of tetrakis(pentafluorophenyl)borate.
• the catalyst system may comprise a compound according to formula 1 carried on a support material, wherein the support material may be selected from a polymeric support material, a clay material, a solid aluminoxane, or an inorganic oxide, preferably wherein the support material comprises silica, alumina or a solid aluminoxanes, such as a solid methyl aluminoxane (MAO).
• Suitable support materials may also include fluorided silica-alumina supports, or sulphated alumina supports.
• Such catalyst system in a supported form may be advantageous for use in certain polymerisation processes, such as in gas-phase homo- or co-polymerisation processes for the production of polymers based on ethylene and propylene.
• such catalyst system may comprise a compound according to formula 1 in unsupported form.
• the support is a silica having a surface area of between 200 and 900 m 2 /g and/or a pore volume of > 0.5 and ⁇ 4.0 ml/g.
• the invention in a further embodiment also relates to a process for the polymerisation of olefins, preferably wherein the polymerisation involves reaction of a reaction mixture comprising ethylene and/or propylene, in the presence of a catalyst system according to the invention.
• Such process may for example be a homopolymerisation process of ethylene, a homopolymerisation process of propylene, a copolymerisation process of ethylene with a comonomer, preferably selected from 1-butene, 1-hexene, 4-methyl- 1-pentene, vinyl cyclohexane, and 1-octene, or a copolymerisation process of propylene with a comonomer, preferably selected from ethylene, 1- butene, 1-hexene, 4-methyl-1-pentene, vinyl cyclohexane, and 1-octene.
• the process may for example be a gas-phase process, a solution process, or a slurry process.
• a main group organometallic compound is present that can act as a scavenger compound to scrub impurities from the polymerisation system that might otherwise adversely affect the catalyst activity.
• X in formula 1 is a halogen, an alkoxide moiety, or an amine moiety
• an additional function of this main group organometallic compound is to substitute X with an organic group, for example to substitute X with an alkyl or aralkyl moiety such as a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, or benzyl moiety.
• main group organometallic compound is particularly advantageous when an activator other than an aluminoxane is used.
• Such main group organometallic compounds are those that are able to exchange at least one of its organic moieties with X in the compounds of the invention.
• organolithium compounds, organomagnesium compounds, organoaluminium compounds,, organozinc compounds, or mixtures thereof may be used as such main group organometallic compound.
• the main group organometallic compound is an organoaluminium compound.
• Suitable organoaluminium compounds are for example trimethylaluminium, triethylaluminium, triisopropylaluminium, tri-n-propylaluminium, triisobutylaluminium, tri-n-butylaluminium, tri-tert-butylaluminium, triamylaluminium, tri-n- hexylaluminium, trioctylaluminium, isoprenylaluminium, dimethylaluminium ethoxide, diethylaluminium ethoxide, diisopropylaluminium ethoxide, di-n-propylaluminium ethyoxide, diisobutylaluminium ethoxide, di-n-butylaluminium ethoxide, dimethylaluminium hydride, diethylaluminium hydride, diisopropylaluminium hydride, di-n-propylaluminium
• aluminoxanes may be used as such main group organometallic compound.
• suitable aluminoxanes are methylaluminoxanes, methyl-isobutylaluminoxanes, isobutylaluminoxanes, and mixtures thereof.
• an active hydrogen means that the hydrogen atom is able to react with the main group organometallic compound.
• Suitable compounds comprising at least one active hydrogen in the context of the present invention are for example alcohol compounds, silanol compounds, and amine compounds.
• Suitable amine compounds are sterically encumbered amine compounds. Examples of sterically encumbered amine compounds are cyclohexylamine or an alkylamine comprising at least one aliphatic group having at least four carbon atoms.
• Suitable alcohol compounds are preferably sterically encumbered alcohol compounds, such as substituted phenolic compounds.
• any substituted mono- or polyphenolic compound may be used.
• Suitable substituted monophenolic compounds are for example butylated hydroxytoluene (BHT, 2,6-di-t-butyl-4-methylphenol), 2,6- di-t-butylphenol, and a-tocopherol (vitamin E).
• BHT butylated hydroxytoluene
• vitamin E 2,6-di-t-butyl-4-methylphenol
• vitamin E a-tocopherol
• the amount of the compound comprising at least one active hydrogen is such that after combining this compound with the main group organometallic compound, the latter still contains organometallic bonds, preferably at least one organometallic bond per main group metal atom.
• the process to produce the olefin polymers may start with the reaction of a compound of the invention and an activator, optionally in the presence of the main group organometallic compound, optionally in the presence of a compound comprising at least one active hydrogen atom, optionally in the presence of a suitable support material.
• This reaction may be performed in the same vessel as the reaction vessel wherein the olefin polymers are produced, or may be a separate vessel. It may be advantageous to combine the inventive compound at first with a portion of the quantity of the main group organometallic compound that is to be used, optionally in the presence of the compound containing at least one active hydrogen, before mixing with the activator.
• the resulting mixture may be fed to a polymerisation reactor.
• an inert solvent may be used.
• the activator may be an aluminoxane-based activator.
• the activator may preferably be used in a quantity of between 10 and 100,000 moles of aluminium, preferably of between 10 and 10,000 moles of aluminium, per mole of the transition metal in the inventive compound.
• aluminoxanes are used as activators, especially methyl-aluminoxanes, it is know that such aluminoxanes may contain residual tri-methylaluminium, sometimes also referred to as free tri-methylaluminium.
• the amount of free tri-methylaluminium is typically specified by the supplier of the aluminoxanes, but it may also be determined by known analytical techniques. It may be suitable to treat such solutions of aluminoxanes with a compound containing at least one active hydrogen, like for example BHT.
• a suitable amount of the compound containing at least one active hydrogen in this case may be expressed as the molar ratio with respect to tri- methylaluminium, for example a molar ratio of active hydrogen to tri-methylaluminium in the range of 3: 1 to 0.1 : 1 , or in the range of 2: 1 to 1 : 1.
• the activator may be an organoboron-based activator.
• the activator may preferably be used in a quantity of between 0.1 and 100 moles of boron, preferably of between 0.5 and 50 moles of boron, per mole of the transition metal in the inventive compound.
• the compound may also be used in catalyst systems that contain a multitude of different transition-metal compounds, for example in a mixed catalyst system. Such a mixed catalyst system that contains a multitude of different transition-metal compounds may for example be used to produce polyolefins with a specific heterogeneity. This heterogeneity may be intra- or inter-molecular in nature.
• a mixture of different transition-metal compounds may be used to produce a mixture of polymers that differ in averaged molecular weight and/or comonomer content.
• a mixture of different transition-metal compounds may be used to produce a polymer that has an intra-molecular heterogeneity in comonomer content, for example a block-copolymer.
• such a mixed catalyst system may be used in a single reactor or in staged reactors.
• staged reactors it may also be that one or more of the inventive compounds is used in just one reactor and the other component of the mixed catalyst system is added to a different reactor of the staged reactors.
• a mixed catalyst system may for example contain one or more conventional Ziegler-Natta catalysts, Phillips type chromium catalysts, metallocenes, post-metallocenes or any other transition-metal compound that catalyses the polymerization of olefins under the applied reaction conditions.
• the solvent that is used may be any organic solvent as is typically used in olefin polymerisation processes.
• the solvent may be benzene, toluene, xylene, propane, butane, pentane, hexane, heptane, cyclohexane, methylcyclohexane, and methylchloride.
• the olefin that is to be polymerised may be used as solvent.
• the polymerisation conditions such as temperature, time, pressure, and monomer concentration may be chosen within wide limits.
• the polymerisation temperature may for example be in the range of between -100°C and 300°C, preferably between 0°C and 240°C, more preferably between 50°C and 220°C.
• the polymerisation time may for example be in the range from 10 seconds to 20 hours, preferably from 1 minute to 10 hours, more preferably from 3 minutes to 5 hours.
• the ethylene pressure may for example be in the range of from 1 to 3500 bar, preferably from 1 to 2500 bar, more preferably from 1 to 1000 bar, even more preferably from 1 to 500 bar, yet even more preferably from 1 to 100 bar.
• the molecular weight of the polymer may be controlled by well-known means such as the use of hydrogen or zinc-alkyls in the polymerisation.
• the polymerisation may be conducted in a batch process, a semi-continuous process, or a continuous process.
• the polymerisation may be conducted in two or more steps of different polymerisation conditions.
• the polymer that is produced may be separated from the solvent that is employed in the polymerisation reaction and from residual monomers and optionally comonomers, and dried by methods known to the person skilled in the art.
• the polymerisation may involve a homopolymerisation of an olefin monomer, or a copolymerisation of an olefin monomer and one or more comonomer(s).
• the olefin monomer may for example be ethylene or propylene.
• the comonomer may for example be ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1 -butene, 3,3,-dimethyl-1-butene, 4-methyl-1- pentene, 3-methyl-1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene; a conjugated or a non- conjugated diene such as butadiene, 1,4-hexadiene, a substituted or unsubstituted norbornene, 5-ethylidene-2-norbornene, vinyl-norbornene, dicyclopentadiene, 4-methyl- 1,4-hexadiene, 1,9- decadiene, or 7-methyl-1,6-octadiene; cyclic olefins such as cyclobutene, cyclopentene; or other olefinic compounds such as isobutene, vinyl-cyclohexane, or sty
• the olefin monomer is ethylene.
• the polymer produced using ethylene as olefin monomer may be referred to as an ethylene homopolymer, or, in case that the polymerisation is a copolymerisation reaction, an ethylene copolymer.
• Such ethylene homopolymers and copolymers may together be referred to as polyethylenes.
• the comonomer is an olefin having 3 or more carbon atoms, for example an olefin comprising 3 to 10 carbon atoms, such as an a-olefin comprising 3 to 10 carbon atoms.
• the comonomer is selected from propene, 1 -butene, 1 -hexene, 1-octene, norbornene, vinyl-cyclohexane, styrene, and 4-methyl-1-pentene.
• the olefin monomer is ethylene
• the comonomer is selected from 1 -butene, 1 -hexene, 1-octene, norbornene, vinyl-cyclohexane, styrene, and 4-methyl-1-pentene.
• the process for the production of olefin polymers using the compounds of the present invention is copolymerisation of an olefin monomer and one or more comonomer(s), wherein the olefin monomer is ethylene, and the comonomer is selected from 1 -butene, 1- hexene, 1-octene, norbornene, vinyl-cyclohexane, styrene, and 4-methyl-1-pentene.
• the process for the production of olefin polymers using the compounds of the present invention is copolymerisation of an olefin monomer and one or more comonomer(s), wherein the olefin monomer is ethylene, and the comonomer is selected from 1 -butene, 1- hexene, 4-methyl-pentene-1, vinylcyclohexane, and 1-octene.
• the polymerisation is a copolymerisation of an olefin and one or more comonomer(s)
• the olefin and the comonomer(s) are different compounds.
• the olefin polymer may for example comprise from 1.0 to 80.0 wt.% of moieties derived from the comonomer, preferably from 5.0 to 60.0 wt%, more preferably from 10.0 to 50.0 wt%, or from 10.0 to 30.0 wt%, with regard to the total weight of the olefin polymer.
• the ethylene copolymer may for example comprise from 1.0 to 80.0 wt.% of moieties derived from the comonomer, preferably from 5.0 to 60.0 wt%, more preferably from 10.0 to 50.0 wt%, or from 10.0 to 30.0 wt%, with regard to the total weight of the ethylene copolymer.
• the polyethylene may for example have a melt mass-flow rate as determined in accordance with ASTM D1238-10 at 190°C at a load of 2.16 kg (MFI2.16) of 3 0.1 and £ 125 g/10 min.
• MFI2.16 melt mass-flow rate
• the polyethylene may have an MFI2.16 of 3 0.1 and £ 50 g/10 min, or 3 0.3 and £ 10.0 g/10 min, or 3 0.5 and £ 5.0 g/10 min.
• the olefin polymer may for example be of very high molecular weight, for example an ultra high molecular weight polyolefin, for example Ultra High Molecular weight Polyethylene, UHMwPE.
• the polyethylene may for example have a density of 3 855 kg/m3 and £ 970 kg/m3, as determined in accordance with ASTM D1505-10.
• the polyethylene may for example have a density of 3 855 and £ 910 kg/m3, or of 3 875 and £ 900 kg/m3.
• the polyethylene may for example have a density of 3 910 and £ 925 kg/m3, or of 3 910 and £ 920 kg/m3, or of 3 915 and £ 920 kg/m3.
• the polyethylene may for example have a density of 3 925 and £ 940 kg/m3, or of 3 930 and £ 940 kg/m3.
• the polyethylene may for example have a density of 3 940 and £ 965 kg/m3, or of 3 945 and £ 960 kg/m3.
• the comonomer is selected from 1 -butene, 1 -hexene, 4- methyl-1-pentene, vinyl-cyclohexane and 1-octene with particularly high incorporation of the comonomer.
• the amount of incorporation of the comonomer may be expressed as the amount of short chain branches per 1000 carbon atoms in the polymer.
• the amount of short chain branches may for example be determined using 13C NMR via the method as described by Randall, Rev. Macromol. Chem. Phys., C. 29, V. 2&3, p. 285-297.
• the ethylene copolymer may for example comprise at least 10, 25, or 80 short chain branches per 1000 carbon atoms in the polymer.
• the ethylene copolymer may comprise at most 200, 100, 50 or 25 short chain branches per 1000 carbon atoms in the polymer.
• the ethylene copolymer may for example comprise at least 10 and at most 200 short chain branches per 1000 carbon atoms in the polymer, or at least 15 and at most 100, or at least 20 and at most 50.
• the polyethylene may have a number-average molecular weight (Mn) of between 1,000 and 10,000,000 g/mol, preferably between 10,000 and 1,000,000 g/mol, more preferably between 20,000 and 500,000 g/mol.
• the polyethylene may have a weight-average molecular weight (Mw) of between 2,000 and 20,000,000 g/mol, preferably between 20,000 and 2,000,000 g/mol, more preferably between 40,000 and 1,000,000 g/mol.
• the Mw and Mn are determined in accordance with ASTM D6474-12, using 1,2,4-trichlorobenzene or o-dichlorobenzene as solvent, and calibrated using polyethylene or polystyrene standards.
• the polyethylene may for example have a molecular weight distribution Mw/Mn of 3 2.0 and £ 5.0, or 3 2.1 and £ 4.0, or 3 2.5 and £ 3.5.
• the numbers in the column LS indicate the general procedures for the ligand synthesis
• the number in the column PS indicates the general procedure for the precursor synthesis, i.e. the compounds of the invention.
• the 48 PPR cells Prior to execution of a library, the 48 PPR cells (reactors) undergo ‘bake-and-purge’ cycles overnight (8 h at 90-140°C, with intermittent dry N 2 flow) to remove any contaminants. After cooling to glove-box temperature (23°C), the stir tops are taken off, and the cells are fitted with disposable 10 ml glass inserts and PEEK stirring paddles, previously hot-dried under vacuum.
• the stir tops are then set back in place, the cells are loaded with the proper amounts of toluene (in the range of 2.0-4.0 ml), 1-hexene (in the range of 0.05-2.0 ml) and a tri-isobutyl- aluminium (TiBAI)/butylated hydroxytoluene (BHT) (1:1 molar reaction product) solution, thermostated at 80°C, and brought to the operating pressure of 1.0 MPa with ethylene, unless otherwise specified in the examples.
• the activator was trityl tetrakis pentafluorophenyl borate (TTB)
• TTB trityl tetrakis pentafluorophenyl borate
• the catalyst injection sequence is as follows: proper volumes of a toluene chaser, a solution of the precatalyst in toluene (typically in the range of 0.005-0.05 mmol/l) and a toluene buffer are uptaken into the slurry needle, and then injected into the cell of destination.
• the reaction is left to proceed under stirring (800 rpm) at constant temperature (80°C) and pressure (1.0 MPa, unless otherwise specified) with continuous feed of ethylene for 5-60 minutes, and quenched by over-pressurising the cell with dry air.
• reaction yields are double-checked against on-line monomer conversion measurements by robotically weighing the dry polymers in a Bohdan Balance Automator while still in the reaction vials, subtracting the pre-recorded tare. Polymer aliquots are then sampled out for the characterisations.
• GPC curves were recorded with a Freeslate Rapid GPC setup, equipped with a set of 2 mixed-bed Agilent PLgel 10 pm columns and a Polymer Chat IR4 detector.
• the upper deck of the setup features a sample dissolution station for up to 48 samples in 10 ml magnetically stirred vials, 4 thermostated bays each accommodating 48 polymer solutions in 10 ml glass vials, and a dual arm robot with two heated injection needles.
• pre weighed polymer amounts typically 1-4 mg
• ODCB orthodichlorobenzene
• BHT 2,6-di-tert-butyl-4-methylphenol
• the samples are transferred to a thermostated bay at 145°C, and sequentially injected into the system at 145°C and a flow rate of 1.0 ml/min.
• the analysis time is 12.5 min per sample.
• Calibration is carried out with the universal method, using 10 monodisperse polystyrene samples (M n between 1.3 and 3700 kg/mol). Before and after each campaign, samples from a known i-PP batch produced with an ansa-zirconocene catalyst are analysed for a consistency check.
• 13 C NMR spectra are recorded with a Bruker Avance 400 III spectrometer equipped with a 5 mm High Temperature Cryoprobe, and a robotic sample charger with a pre-heated carousel (24 positions).
• the samples (20-30 g) are dissolved at 120°C in tetrachloroethane-1,2-d2 (0.6 ml), added with 0.40 mg/ml of BHT as stabiliser, and loaded in the carousel maintained at the same temperature.
• the spectra are taken sequentially with automated tuning, matching and shimming.
• Typical operating conditions for routine measurements are: 45° pulse; acquisition time 2.7 s; relaxation delay 5.0 s; 400-800 transients (corresponding to an analysis time of 30- 60 min). Broadband proton decoupling is achieved with a modified WALTZ16 sequence (BI_WALTZ16_32 by Bruker).
• the experiments were conducted at a total reactor pressure of 0.9 MPa, using a 1-hexene concentration of 1.0 vol% in the diluent, at 80°C, using methylaluminoxane (MAO) as activator.
• the MAO was pretreated with BHT in such amount that the molar ratio of BHT to the residual amount of tri-methylaluminium in the MAO was 2:1.
• the aluminium (from the MAO solution) concentration in the reactor was 2 mmol/l.
• copolymerisations of ethylene with vinyl cyclohexane illustrate the desirably high incorporation of the sterically encumbered olefins by using the inventive compounds as catalysts.
• Comparative examples were conducted using the compounds C-1 and C-2 in ethylene/ VCH copolymerisations according to the conditions as set out above, the result of which are presented in the table below.
• the compound 1-18 was used in copolymerisation experiments using different activators and different chain transfer agents (CTA) at a total pressure of 1.0 MPa in the reactor and using 2 vol% hexene as comonomer at 80°C.
• CTA chain transfer agents
• boron-containing activator N,N- dimethylanilinium tetrakispentafluorphenylborate (AB) was used in a B/Zr molar ratio of 2, in combination with 1 mmol/l TiBAI.
• CTA hydrogen or diethylzinc (ZnEt2) was used. Diethylzinc was used in two different molar ratios of Zn/Zr.

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